EP0177490A1 - Polymeres de polysulfures de (vinylaryle)alcoyle - Google Patents

Polymeres de polysulfures de (vinylaryle)alcoyle

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Publication number
EP0177490A1
EP0177490A1 EP84901538A EP84901538A EP0177490A1 EP 0177490 A1 EP0177490 A1 EP 0177490A1 EP 84901538 A EP84901538 A EP 84901538A EP 84901538 A EP84901538 A EP 84901538A EP 0177490 A1 EP0177490 A1 EP 0177490A1
Authority
EP
European Patent Office
Prior art keywords
polymer
vinylaryl
alkyl
polysulfide
polymers
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP84901538A
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German (de)
English (en)
Other versions
EP0177490A4 (fr
Inventor
Victor Eugene Meyer
Thomas Edward Dergazarian
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Dow Chemical Co
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Dow Chemical Co
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Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Publication of EP0177490A1 publication Critical patent/EP0177490A1/fr
Publication of EP0177490A4 publication Critical patent/EP0177490A4/fr
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/04—Polysulfides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F12/34—Monomers containing two or more unsaturated aliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/14—Polysulfides
    • C08G75/16—Polysulfides by polycondensation of organic compounds with inorganic polysulfides

Definitions

  • This invention relates to polysulfide polymers.
  • Polysulfide polymers are well-known and have been used commercially for many years. See, for example, U.S. Patent Nos. 1,890,191 and 2,466,963.
  • Such polysul- fide polymers are prepared by copolymerizing metal polysulfides and polyfunctional aliphatic hydrocarbons such as ethylenedichloride, 1,2,3-trichloropropane and bis 2-chloroethyl formal. A very high molecular weight rubber is thereby formed, which is then cleaved with sodium hydrogen sulfide and sodium sulfite to yield a lower molecular weight mercaptan-terminated polymer.
  • these mercaptan-terminated polymers may be cured by the use of oxidants such as metal oxides to form rubbers with many desirable properties, the mercaptan end groups of these polymers impart a strong, disagreeable odor which limits the practical utility of these polymers.
  • Styrene is also known to react with sulfur to produce a high molecular weight polymer, but it rapidly depolymerizes to give 2,4-diphenylthiophene. See Blight et al., Adv. Chem. Ser. 165 13 ⁇ 1978).
  • This invention is a curable polysulfide polymer which has little or no odor.
  • the polymers of the present invention are polysulfide polymers having the general structure:
  • each R is independently a polyvalent organic polyradical with each valence residing on a carbon atom; each Z is independently (vinyl ryl)alkyl, inertly substituted (vinylaryl)alkyl or a noncrosslinking monoradical, provided that a sufficient proportion of Z contain a vinyl aryl moiety to enable the polymer to cure to a material that does not cold flow; 1 and m are independently zero or a positive integer; ⁇ is a number from about 2 to about 8 provided that when m is zero ' and each Z is vinylbenzyl then n is at least 3; and p is zero or a positive integer which is the difference between the valence of R and two.
  • this invention is a process by which curable polysulfide polymers are produced wherein desirable properties, i.e., molecular weight, curing properties and branching, are selectively imparted to the polymers.
  • Said process comprises reacting a polysulfide salt of an alkali or alkaline earth metal with (vinylaryl)alky1 compound as described hereinafter and at least one inertly substituted polyfunctional organic compound having a plurality of negatively charged functionalities which will split off upon reacting with the metal polysulfide.
  • the present invention is a curable, water-resistant, polysulfide caulking composition and an adherent, polysulfide window sealing composition.
  • the (vinylaryl)alkyl-terminated polysulfides of this invention are advantageously produced by the reaction of a metal polysulfide and a (vinylaryl)alkyl compound having negatively charged functionality which will split off upon reacting with the metal polysulfide.
  • Metal polysulfides useful in the practice of this invention are soluble polysulfides of a mono- or diva ⁇ lent metal cation which forms a bond with the polysul ⁇ fide which is primarily ionic in character, i.e. dis- sociates in water.
  • Particularly useful metal polysul ⁇ fides are those of calcium, magnesium, lithium, potas ⁇ sium and sodium. Of these, sodium polysulfides are most preferred on the basis of cost and availability.
  • Said metal polysulfides are prepared by reacting a dissolved metal monosulfide with elemental sulfur and refluxing the mixture to form the desired polysulfide.
  • the desired polysulfides are prepared by reacting anhydrous metal sulfides with molten sulfur or by reacting aqueous sodium hydroxide with elemental sulfur. See "Encyclopedia of Chemical Technology," 2d Ed., V. 16, page 255. The process by which the metal polysulfides are generated is a matter of choice to the practitioner of this invention, and should not be construed as critical to the practice of this invention.
  • the number of sulfur atoms in the polysulfide chain is referred to in the art as the sulfur "rank.”
  • the rank of the polysulfide chains is controlled by varying the proportions of the metal sulfide and elemen- tal sulfur employed to form the metal polysulfide. By increasing the proportion of elemental sulfur to the metal sulfide, the average rank of the resulting poly ⁇ sulfide is increased. In the formation of the polysul ⁇ fide by the reaction of NaOH .with elemental sulfur, longer sulfur chains are formed by increasing the temperature at which the reaction is carried out. However, precise control of the sulfur rank is not achieved by any of these processes and the polysulfide chains so produced will have varying ranks.
  • the "rank" of the sulfur chains produced represents only a number average of the actual individual ranks, and it is understood that said actual individual ranks will vary, usually between 2 to about 8, with the majority of the polysulfide chains having ranks within one of the designated rank.
  • a polysulfide with a desig ⁇ nated sulfur rank of 4 will have individual polysulfide chains having from 2 to about 8 sulfur atoms, with most of the polysulfide chains having 3, 4 or 5 sulfur atoms.
  • the sulfur rank is in the range from about 2 to 8, with 2 to 4 being preferred.
  • the metal polysulfide is reacted with a (vinylaryl)alkyl compound represented by the formula:
  • V-Ar-Y-X wherein Ar is an unsubstituted or inertly substituted arylene group such as phenylene, naphthylene, phenanthry- lene, biphenyl and the like, V is an unsubstituted or
  • O P ⁇ inertly substituted vinyl group Y is an alkylene group and X is a negatively charged functionality which will split off upon reacting with the metal polysulfide in the reaction mixture.
  • inertly substituted is meant that the subst ⁇ tuent group does not chemically react under the conditions of the polymerization reaction or the subsequent ' curing of the polymer.
  • Exemplary inert substituents include alkyl groups or either the vinyl or arylene groups, or halogen substituents on the aromatic ring.
  • Y may be a straight chain, cyclic or branched alkylene group, although straight chained groups having fewer than 8, preferably fewer than 5, most preferably 1, carbon atoms are preferred. More preferably, the (vinylaryl)alkyl compound is vinylbenzyl chloride, bromide or iodide, with the chloride being most preferred.
  • Polysulfide polymers are formed by- intro ⁇ ducing, in addition to the (vinylaryl)alkyl compound, an organic compound having a plurality of negatively charged functionalities attached to aliphatic or cyclo- aliphatic carbon esters which functionalities will split off upon reacting with the metal sulfide in the reaction mixture.
  • the term "negatively charged functionality” means a functional group which will split off on reacting with the metal polysulfide to form an anionic species in solution.
  • the functional group is not necessarily ionically bonded to the aliphatic hydrocarbon or (vinylaryl)alkyl compound, and, in fact, is generally covalently bonded thereto.
  • the polymerization of polysulfides and polyfunctional organic compounds are well known in the art and is first described in U.S. Patent No. 1,890,191 to Patrick. Suitable polyfunctional compounds include alkyl dihalides,
  • V-Ar-Y-(SnR )mSnY-Ar-V wherein m is a positive integer, n, Ar, V and Y are as defined hereinbefore and R represents an organic diradical, with each valence residing on a carbon atom, which is the residue of the difunctional hydrocarbon after the splitting off of the negatively charged functionalities.
  • chlorides are preferred as the negatively charged functional group due to the facility of their reaction with metal polysulfides, their relatively low cost and high availability.
  • the R group and correspondingly, the polyfunctional organic compound, may further contain substituents which are inert under the conditions of the polymerization reac ⁇ tion and may further incorporate linkages such as ether, sulfide, alkene or arylene into the chain.
  • those polyfunctional monomers previously known to react with metal polysulfides to form polymers therewith are also suitably employed in this invention.
  • Preferred polyfunctional monomers include dichloro- ethane, 1,2,3-trichloropropane, bis-2-chloroethyl formal, bis-4-chlorobutyl ether, bis-4-chlorobutyl formal and l,3-dichloro-2-propanol.
  • polyfunc ⁇ tional monomers which are illustrative of the wide scope of monomers suitably employed herein include, for example, bis(4-chloromethyl)phenyl ether, bis(4-chloro- acetyl)phenyl ether, 2,5'-di(chloromethyl)l,4-dioxane and diethylene glycol bis(chloroacetate) .
  • Trifunctional, tetrafunctional and pentafunc- tional organic compounds such as 1,2,3-trichloropropane and the like, may be employed in conjunction with difunctional hydrocarbons and will polymerize with the polysulfide and the (vinylaryl)alkyl compound to form a branched polymer as represented by the general structure:
  • each R is independently a polyvalent organic polyradical with ' each valence residing on a carbon atom, and p is zero or a positive number which is the difference between the valence of R and two. It is noted that each R is the residue formed by the splitting off of the negatively charged functionali ⁇ ties from the respective difunctional and polyfunctional hydrocarbons.
  • the amount and degree of branching of the polymer is selectively determined by the choice and relative proportion of the organic monomers employed in the reaction.
  • a branched chain may be formed as desired.
  • suitably branched polysulfide polymers are produced by employing from 90 to 99.5 weight percent of a difunctional monomer and from 10 to 0.5 weight percent of a monomer having at least three functionalities, said percentages being based on the total weight of all the polyfunctional monomers employed in the reaction. If high modulus and low cold flow in the cured polymer are desired, from about 2 to 10 weight percent, preferably from 3 to 5 weight percent, of a monomer having at least three functionalities is
  • OMPI employed, said percentages being based on the total weight of all the polyfunctional monomers employed in the reaction. If the polymer is to be employed as a sealant, from about 0.5 to about 4 weight percent of a monomer having at least 3 functionalilites is bene ⁇ ficially employed.
  • the polyfunctional monomer is chosen such that the polymer produced therefrom has the desired physical properties.
  • Many of the beneficial properties of polysulfide polymers such as resistance to oxygen permeation, water, ultraviolet light and solvents are generally attributable to the polysulfide segments of the polymer.
  • properties such as high elongation, flexibility, and increased solubility are selected to be imparted to the polymers primarily by the organic segments.
  • the properties of the polymers of this invention can be selectively deter ⁇ mined by the choice of organic monomers and the rank of the polysulfide segments.
  • a high sulfur polymer can be produced by employing low molecular weight organic compounds, such as bis-2-chloromethyl formal, 1,2,3-trichloropropane or ethylene dichloride.
  • organic compounds such as bis-2-chloromethyl formal, 1,2,3-trichloropropane or ethylene dichloride.
  • polysulfides of varying rank may be employed to selectively vary the carbon to sulfur ratio in the polymeric chain.
  • the reaction is suitably carried out by heating the aqueous polysulfide solution from about 25° to about 90°C, preferably from about 50° to about 80°C, and adding the organic monomer and the (vinyl ryl)alkyl compound over a period of about 5 minutes to 2 hours.
  • the mixture is then heated at 25° to 90°C, preferably from about 50° to about 80°C, for about 1 to 3 hours to form the desired (vinylaryl)alkyl-terminated polysulfide.
  • the organic reactants are advantageously intermixed with the aqueous phase to facilitate the reaction.
  • Said intermixing may be is achieved by adjusting the density of the aqueous phase to approximate that of the organic phase or by forming an emulsion.
  • An emulsion can be created by the addi- tion of a suspending agent such as magnesium hydroxide in conjunction with a surfactant such as sodium lauryl sulfate or other organic surfactants such as alkylated sulfonated phenyl ethers.
  • the suspended organic phase thus reacts more readily with the dissolved polysulfide to form the desired (vinylaryl)alkyl-terminated polysul ⁇ fide.
  • the product is recovered by breaking the emulsion. This may be done by adding water and acid to adjust the pH to about 2 to 6, prefer ⁇ ably from about.3 to 5. Alternatively, the product may be recovered by adding an organic solvent such as acetone, or by mechanical means such as centrifugation, or combinations thereof.
  • Means for recovering organic products from an emulsion are well known in the art and are not considered critical to the invention. It may be preferred, for some applications, not to recover the polymer from the emulsion, but instead employ the polymer in the form of a latex.
  • the molecular weight of the polymer is controlled.
  • Molecular weight of the polymers formed according to this invention increases as the proportion of the (vinylaryl)alkyl compound is decreased.
  • curable polymers of the desired molecular weight may be produced in a single reaction.
  • the polymers of this invention have a theoretical molecular weight, as calculated from the relative proportions of the reactants employed, of at least about 490, preferably from about 3,000 to about 200,000, more preferably from about 5,000 to about 25,000.
  • molecular weight control in previ ⁇ ously known processes for producing polysulfide resins cannot be achieved during the polymerization reaction, said control of the molecular weight represents a significant step forward in the art.
  • control of the molecular weight in the polymerization reaction obviates the need for the cleavage step required in the formation of previously known polysul ⁇ fide resins. Because the cleavage step in the prior art introduces terminal mercaptan groups to the resins thus produced, the elimination of this step produces a polymer free of the objectionable odors of previously known polysulfide resins.
  • the amount of crosslinking in the cured polymer is also controlled by the proportion of the (vinylaryl)alkyl compound employed in the polymeriza ⁇ tion reaction. While the precise mechanism of the curing reaction is not known, infrared studies indicate that curing is effected by cleavage of the polysulfide linkages, and subsequent reaction of the terminal sulfur radicals with the vinyl group in a rearrangement reaction to produce a highly crosslinked cured polymer. Thus, by reducing the amount of (vinylaryl)alkyl groups in the polymer, fewer crosslinks will be formed in the cured polymer. However, a sufficient proportion of the terminal groups of the polymer must be (vinylaryl)alkyl
  • cold flow is meant that when the cured material is pressed onto a sheet of glass, said material will not flow under its own weight when the glass is held in a vertical position.
  • a portion of the (vinylaryl)alkyl compound may be replaced with a noncrosslinking monofunctional organic compound having a single negatively charged function ⁇ ality which splits off upon reacting with the metal polysulfide.
  • Said noncrosslinking monofunctional organic compounds will become terminal groups of the polymers, thereby providing molecular weight control.
  • these monofunctional compounds are noncrossiinking, i.e., have no aliphatic carbon-carbon double bonds or other moieties which can cause cross- linking when the polymers are cured, reduced cross- linking in the cured resin can be achieved with coinci- dent control of the molecular weight of the uncured resin.
  • Substitution of a noncrosslinking monofunc- tional organic compound for a portion of the (vinyl ⁇ aryl)alkyl compound yields a polymer of the general form:
  • OMPI_ for in this reaction as well as species in which all terminal groups are (vinylaryl)alkyl, their relative proportions thereof being determined by the relative proportions and reactivity of the (vinylaryl)alkyl compound and the noncrosslinking monofunctional organic compound employed in the reaction mixture. It is preferred that the reactivity of the (vinylaryl)alkyl compound and the noncrosslinking monofunctional compound be roughly comparable. For this ' reason, benzyl chloride is highly preferred as the noncross ⁇ linking monofunctional organic compound when vinyl- benzyl chloride is employed as the (vinylaryl)alkyl compound.
  • the (vinylaryl)alkyl compound is essential for the curing of the polymers of this invention, a sufficient proportion of the terminal groups of the uncured polymers should be (vinylaryl)- alkyl so that the cured polymer will be sufficiently crosslinked that the cured polymer does not cold flow. In general, at least 10 percent, by number, of the terminal groups of the uncured polymer should be (vinylaryl)alkyl.
  • Curing of the polysulfide polymers of this invention is readily effected by heating. Curing time is dependent on temperature; at 140°C complete curing takes from about 10 to 30 minutes whereas curing at
  • Room temperature curing may be induced by combining the polysulfide polymer with such commonly known free-radical initi ⁇ ators as metal peroxides, organic peroxides, especially benzoyl peroxide and cumene hydroperoxide, or ultra ⁇ violet active curing agents such as the butyl ether of benzoin.
  • free-radical initi ⁇ ators as metal peroxides, organic peroxides, especially benzoyl peroxide and cumene hydroperoxide, or ultra ⁇ violet active curing agents such as the butyl ether of benzoin.
  • OMPI A surprising aspect of this invention is that room temperature curing is greatly enhanced if hydroxy functionalities are introduced into the polymer chain. Hydroxy functionalities are preferably introduced into the polymer chain by employing as one of the organic monomers a polyfunctional hydroxy-containing organic compound, such as l,3-dichlor-2-propanol. Significantly improved room-temperature curing is effected when about 1 to about 100 percent, by number, of the organic segments in the polymer contain at least one hydroxy group.
  • the polymers of this invention are readily adapted to a wide variety of uses.
  • Said poly ⁇ mers are useful coatings for materials such as wood, metal, glass, concrete and synthetic fibers as well as for absorbent materials such as textiles, paper, leather and the like.
  • articles such as hoses, sheets, rollers, tanks, gaskets, wire insulation and the like may also be fashioned from said polymers.
  • Said polymers are also useful as components in caulking and sealing compositions. Due to their low odor, the polymers of this invention may be used in household and other populated environments where the odor of previ ⁇ ously known polysulfide polymers precludes their use.
  • the polymers of this invention Due to their good adhesion to glass and resistance to solvents, water and gases, the polymers of this invention have particular applications as sealants and in caulking compositions.
  • Low modulus, highly extensible polysulfide polymers of this inven ⁇ tion i.e., those which are lightly-branched and/or
  • ⁇ PO lightly crosslinked when cured are most beneficially employed in sealant compositions.
  • Plasticizers, fillers, pigments and the like may be beneficially employed in the sealant compositions according to this invention.
  • adhesion is further increased by the incor ⁇ poration of about 0.1 to about 5 weight percent of a coupling agent.
  • exemplary coupling agents include organosilane coupling agents such as mercaptopropyltri- methoxysilane and
  • H 2 C C-C-0(CH 2 ) 3 Si(OCH 3 ) 3 CH 3
  • the sealants of the present invention exhibit excellent water and solvent resistance and gas impermeance.
  • Water-resistant caulking compositions are also prepared from the polymers of this invention.
  • Polysulfide polymers of this invention which, when cured, exhibit high water-resistance, good adhesion, minimal cold flow and which cure relatively quickly at room temperatures are especially suitable for use in caulking compositions.
  • the polymers of this invention do not support fungal growth. For this reason, the polymers of this invention have an advantage over previously known caulking compositions, which must usually be compounded with a fungicide to inhibit fungal growth thereon.
  • vv ' IrO various inert fillers such as fibers, wood flour, carbon black, asbestos, glass, inorganic pigments and the like.
  • Example 1 Preparation of Divinylbenzyltetrasulfide A 96-g portion of hydrated disodium sulfide is dissolved into 100 g of water in a flask equipped with an agitator, a reflux condenser and a means for temperature control. A 37.5-g portion of precipitated sulfur is added and heated at reflux for 1 hour to produce a disodium polysulfide of average composition, Na "" ssSS ' Na . The mixture is then cooled to 70°C and 8.5 g of hydrated magnesium chloride, 3.6 g of sodium hydroxide and 10 g of 30 percent sodium lauryl sulfate is added.
  • VBC vinylbenzyl chloride
  • a 1.5 mil coating of the divinylbenzyl tetra- sulfide thus obtained is coated onto a steel panel and
  • Hardness tester with a 400 g loading.
  • the baked coating exhibits a Knoop hardness of 32.
  • the baked coating is tested for resistance to moisture by placing the coating into a humidity chamber at 15.0°C for 24 hours. No visible effect is noted.
  • Disodium tetrasulfide is prepared as in
  • Example 1 The disodium tetrasulfide is heated to 70°C and 8.5 g MgCl 2 •6 H 2 0, 3.6 g of sodium hydroxide and 10 g of 30 percent sodium lauryl sulfate is added to the mixture. Over a period of 1 hour, 30.5 g of VBC and 29.7 g of ethylene dichloride are added, followed by heating the mixture with agitation for V_ hours. The emulsion is then broken by the addition of 1000 ml of water and 10 ml of glacial acetic acid.
  • the recov ⁇ ered product (78 g) is a viscous oil insoluble in tetrahydrofuran, methyl ethyl ketone, methylchloroform and methyl chloride. Curing is effected by heating the product to 140° to 250°C.
  • Disodium tetrasulfide is prepared by heating a mixture of 216 g Na 2 S*9 H 2 0, 87 g precipitated sulfur and 500 g water at reflux for one hour. The mixture is then cooled to 80°C and 10 g NaOH, 8.5 g MgCl 2 *6 H 2 0,
  • the emulsion is broken by the addition of 2000 ml water and 10 ml glacial acetic acid.
  • the recovered product is dried overnight at 50°C under vacuum and a yield of 132.1 g of a lightly branched, low odor polymer is obtained.
  • the curing behavior of the polymer is measured by placing 8 g of the polymer into a Monsanto oscillating disc rheo eter, heating to 140°C and measuring the change in torque imparted by the polymer on the oscillat ⁇ ing disc as a function of time. An increase in the torque is indicative of curing of the polymer. After 5 minutes at 140°C, the torque increases, indicating that curing has begun. After about 35 minutes, no futher increase in torque is seen, indicating that complete curing has occurred.
  • the glass adhesion properties of the polymer are tested in the following manner: A quantity of the polymer is mixed with 2.5 weight percent fumed silica, - a thixotropic filler. This mixture is then divided into 4 parts, designated samples A, B, C and D. To samples B and D is added 2.5 .weight percent of a mercap- topropyltrimethoxysilane coupling agent. Samples C and D are then further prepared for testing by forming
  • Sample B is tested in the same manner as Sample A.
  • Samples C and D are tested by placing a 0.5 mil film of the cured samples between 2 glass slides, and heating at 140°C for 30 minutes to effect adhesion of the film to the slides. Lap strength and percent elongation are then tested as in Sample A.
  • Sample 0 a commercially available silicone sealant sold by the Dow Corning Corporation under the trade designation Dow Corning Silicone Rubber Sealant, is tested in the same manner as Sample A, except curing was effected by allowing to stand at room temperature for 24 hours.
  • Sample B exhibits significantly improved adhesion and elongation. It is further seen that adequate adhesion and elongation are obtained when the sealants of this invention are cured in situ or when a precured sample is heat-adhered to the glass.
  • Example 3 The reaction of Example 3 is repeated, this time substituting 1.0 g benzyl chloride and 5.0 g of VBC for the 6.0 g VBC employed in Example 3.
  • the uncured resin has an extensibility of about 2000 percent as measured in an Instron tensile tester at a strain rate of 2 inches per minute. Curing of the polymer is effected in 15 minutes at 140°C as measured by a Monsanto rheometer. After curing, the resin has an extensibility of about 400 percent.
  • a caulking formulation is prepared by mixing 8.0 g of the above uncured resin, 1.6 g dioctylphtha- late and 0.4 g fumed silica.
  • An off-white caulk is obtained which is extensible to 1000 percent as measured in an Instron tensile tester at a strain rate of 2 inches per minute and does not cold flow when pressed onto glass and held in a vertical position.
  • Example 5 The reaction of Example 3 is again repeated, this time using 2.0 g VBC and 6.0 g benzyl chloride instead of the VBC employed in Example 3.
  • VBC 6.0 g benzyl chloride
  • OMPI _ il-O been heated do not cold flow.
  • the decreased tackiness and cold flow of the heated samples indicates that some curing does occur upon heating.
  • These lightly cross ⁇ linked samples exhibit elongation to 1000 percent as measured in an Instron tensile tester at a strain rate of 2 inches per minute.
  • a quantity of disodium tetrasulfide is prepared as in Example 1, and maintaining the temperature at 70°C, l.O g of a sodium salt of a dodecylated, sulfonated phenyl ether surfactant, 3.6 g NaOH and 8.5 g MgCl 2 *6 H 2 0 are added. To this mixture are added 30.5 g VBC, 9.9 g ethylene dichloride and 25.8 g l,3-dichloro-2-propanol. This mixture is then heated to 70°C for one hour. The product is recovered by the addition of 1000 ml of water and 10 g of acetone, followed by drying overnight at 50°C under vacuum. The product is a very viscous, rubbery oil having the general formula:
  • O P ⁇ coated onto a glass slide The coating is only slightly tacky after drying for 3 hours at room temperature and after 24 hours becomes a tack-free, enamel-like coating.
  • Example 7 (Comparative) The reaction of Example 6 is repeated, substi ⁇ tuting 33.7 g of benzyl chloride for the VBC used in Example 6 and 34.4 g. l,3-dichloro-2-propanol for the ethylene dichloride and the 1,3-dichloro-2-propanol employed in Example 7.
  • the product is a very viscous, rubbery oil.
  • a quantity of disodium tetrasulfide is prepared as in Example 1.
  • the disodium tetrasulfide mixture is cooled to 70°C and an emulsion is formed by the addition of 5.0 g of a 45 percent solution of a sodium salt of a dodecylated sulfonated phenyl ether, 3.6 g NaOH and 8.5 g MgCl 2 *6 H 2 0. While maintaining the mixture at 70°C, 0.8 g VBC and 35.8 g ethylene dichloride is added over the period of 1 hour.
  • the mixture is then heated at 70°C for an additional hour, followed by the addition of 1000 ml of water and 10 g HCl to break the emulsion.
  • An oily, rubbery product is recovered and dried under vacuum for 24 hours at 50°C.
  • the dried polymer- is tested for resistance to fungal attack in the following manner: a 1 mm film of the polymer is cast onto a glass slide and cured at
  • Example 8-B sterile filter paper discs
  • Example 8-C a l cm x l c l mm film of a commercially available silicone sealant sold as Dow Corning Silicone Rubber Sealant, cured at room tempera ⁇ ture for 24 hours
  • Example 8-D a commercial preparation containing a fungicide, cured at.27°C for 24 hours
  • test material provides the sole source of carbon available for fungal growth This test is a modification of ASTM G21-70. Ratings for visible growth of fungi recommended by ASTM:
  • the cured polymer of this invention does not support any visible fungal growth.
  • the commer ⁇ cial bathtub caulk containing a fungicide supports as little fungal growth as the present invention.

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Sealing Material Composition (AREA)

Abstract

Polysulfures de di(vinylaryle)alcoyle et copolymères de polysulfures à terminaison (vinylaryle)alcoyle à odeur réduite et polymérisables, de structure générale (I) où n est un nombre entier de 2 à 8, l et m sont des nombres entiers positifs, chaque R représente indépendamment un polyradical organique avec les radicaux situés sur les atomes de carbone, p vaut 0 ou représente un nombre entier positif qui est la différence entre le nombre de radicaux sur R et 2, chaque Z est choisi indépendamment dans la classe formée par le (vinylaryle)alcoyle et d'autres monoradicaux de non-réticulation, à condition qu'une proportion suffisante des groupes Z représente un (vinylaryle)alcoyle, si bien que le polymère, une fois polymérisé, ne subit pas de fluage à froid. Sont en outre décrits un procédé de préparation desdits polymères, ainsi que des compositions utiles de calfatage, d'étanchéité et d'adhérence preparées à partir de ceux-ci.
EP19840901538 1982-01-18 1984-03-20 Polymeres de polysulfures de (vinylaryle)alcoyle. Ceased EP0177490A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US33982082A 1982-01-18 1982-01-18
US06/426,559 US4438259A (en) 1982-01-18 1982-09-29 (Vinylaryl)alkyl polysulfide polymers

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EP0177490A1 true EP0177490A1 (fr) 1986-04-16
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EP19840901538 Ceased EP0177490A4 (fr) 1982-01-18 1984-03-20 Polymeres de polysulfures de (vinylaryle)alcoyle.

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US4438259A (en) * 1982-01-18 1984-03-20 The Dow Chemical Company (Vinylaryl)alkyl polysulfide polymers
US4608433A (en) * 1982-01-18 1986-08-26 The Dow Chemical Company Inert monovalent hydrocarbon terminated polysulfide polymers
US4607078A (en) * 1983-11-16 1986-08-19 The Dow Chemical Company Blends of organic polymers and organic terminated polysulfide polymers
FR2598711B1 (fr) * 1986-05-13 1988-09-16 Inst Nat Rech Chimique Produits polymeres soufres a squelette polymere principal et residus pendants lineaires ou ramifies relies a une ou plusieurs de leurs extremites audit squelette, leur procede de fabrication et leurs applications a l'extraction et/ou a la separation des metaux lourds
US4755570A (en) * 1986-07-07 1988-07-05 The Dow Chemical Company Polysulfide modified epoxy resins
US4692500A (en) * 1986-07-07 1987-09-08 The Dow Chemical Company Polysulfide modified epoxy resins
FR2647796B1 (fr) * 1989-05-31 1991-09-13 Bp Chem Int Ltd Procede de fabrication de nouveaux polymeres comportant des chaines derivees d'un polybutene
US7217846B2 (en) * 2002-10-31 2007-05-15 Atwood Jerry L Calixarene-based guest-host assemblies for guest storage and transfer
RU2496803C1 (ru) * 2012-02-17 2013-10-27 Открытое акционерное общество "Казанский завод синтетического каучука" (ОАО "КЗСК") Синтетический латекс и способ его получения
CN103788372B (zh) * 2013-12-27 2016-01-20 北京彤程创展科技有限公司 一种含有多硫醚结构的聚合物及其制备方法

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US4438259A (en) * 1982-01-18 1984-03-20 The Dow Chemical Company (Vinylaryl)alkyl polysulfide polymers

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US4438259A (en) * 1982-01-18 1984-03-20 The Dow Chemical Company (Vinylaryl)alkyl polysulfide polymers

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JOURNAL OF POLYMER SCIENCE/POLYMER CHEMISTRY EDITION, vol. 18, no. 2, February 1980, pages 383-406, John Wiley & Sons, Inc., New York, US; B.K. BORDOLOI et al.: "Copolymerization of liquid sulfur with certain olefinic systems and structure-property studies on the polymeric materials" *
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WO1985004177A1 (fr) 1985-09-26
EP0177490A4 (fr) 1986-09-04

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